Process for hydrogenation of olefins



United States Patent O 3,542,898 PROCESS FOR HYDROGENATION OF OLEFINS Walter A. Butte, In, West Chester, Pa., assignor to Sun Oil Company, Philadelphia, Pa., a corporation of New Jerse No Dra wing. Original application Dec. 21, 1967, Ser. No. 692,288. Divided and this application Aug. 22, 1969, Ser. No. 870,736

Int. Cl. C07c /02 US. Cl. 260-6833 5 Claims ABSTRACT OF THE DISCLOSURE New catalysts useful for the dimerization, isomerization and hydrogenation of olefins such as aliphatic monoolefins and diolefins are formed by admixing, in the presence of a mutual solvent, a hydrocarbyl lithium compound of the formula LiR, wherein R is a hydrocarbon radical having 1-30 carbon atoms selected from the group consisting of alkyl and cycloalkyl, with a cobalt acetylaeetonate of the formula Co[CH(COCH wherein n has a value of 2 or 3.

CROSS REFERENCE TO RELATED APPLICATION This is a division of application Ser. No. 692,288, filed Dec. 21, 1967.

BACKGROUND OF THE INVENTION The dimerization of ethylene employing a catalyst system consisting of a mixture of cobalt compounds and organo-aluminum compounds is disclosed in Chemistry and Industry of Jan. 30, 1965, page 223. As cobalt compounds, cobalt (III) acetylacetonate, cobalt (II) acetylacetonate, and cobalt (II) acetate can be used. Among the elfective organo-aluminum compounds are triethylaluminum, diisobutylaluminum hydride, ethoxydiethylaluminum, and sodium tetraethylaluminate. The catalyst is prepared by mixing both components in an appropriate solvent under nitrogen or ethylene atmosphere. Isomerization of butene-l to butene-2 was noted.

The present invention is based, among other things, upon the discovery that LiR compounds can be used advantageously with selected cobalt compounds, to the exclusion of organo-aluminum compounds.

The catalysts of the invention are highly selective, minimizing side reactions such as skeletal isomerization, cracking and polymerization. Being soluble, they are not subject to deactivation by deposition of solids.

SUMMARY OF THE INVENTION The invention resides in new catalyst complexes resulting from the admixture in a mutual solvent of a hydrocarbyl lithium compound of the formula LiR, wherein R is a hydrocarbyl radical having 13() carbon atoms selected from the group consisting of alkyl and cycloal-kyl, with a cobalt acetylacetonate of the formula wherein n has a value of 2 or 3.

The invention also resides in the use of the foregoing new catalysts in the dimerization, isomerization and hydrogenation of olefins such as aliphatic monoolefins and diolefins, dimerization being very largely confined to ethylene, and to C to C diolefins, e.g., butadiene and its simple homologues, such as isoprene, piperylene and 2,3- dimethylbutadiene.

Catalyst activity is improved when the above-mentioned admixture of catalyst components takes place in the presence of an olefin, e.g., ethylene. In any case, for best 3,542,898 Patented Nov. 24, 1970 ice results, air and certain of its normal components, e.g., oxygen and moisture are excluded.

The mutual solvent for catalyst component admixture purposes can be the olefin or diolefin to be treated for dimerization, isomerization and/or hydrogenation purposes. Good practice dictates that other solvents ought to be inert for practical purposes in the reaction zone, benzene, toluene, xylene, hexane, cyclohexane and the like including mixtures thereof being examples.

While considerable latitude is available in the atomic ratio of lithium to cobalt in the catalyst complex, particularly in the case of isomerization, for good practical purposes this ratio ought to be held to from 47, preferably 5-7, e.g., 6.0 or thereabouts, When n is 3, and from 3-5, preferably 4 or thereabouts, when n is 2.

The following are examples of suitable R groups for the -LiR component of the catalyst complex: ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-amyl, isoamyl, nor isooctyl, nor isodecyl, lauryl, cyclopentyl, methylcyclohexyl and the like. Preferably, LiR is an alkyl lithium in which the alkyl group has 2-10 carbon atoms.

Temperature conditions during reaction in the formation of the catalyst complex and/or in its use are not particularly critical, but ought to be high enough for the reaction to take place at a reasonable rate, and not so high as to cause unwanted decomposition. Temperatures at 0 C. and 30 C. were found quite suitable, whereas at C. reaction was very slow. A good practical range is 0-60 C. At much higher temperatures the catalyst tends to decompose.

When using the catalyst complex, pressures on normally gaseous reactants, or on reactants gaseous under the temperature conditions of reaction, are normally made sufliciently high for the reaction to take place at a reasonable rate, and normally are not so high as to incur un necessary inconvenience or hazard. For example, when dimerizing ethylene, pressures in the range of 0.1 to atmospheres, and particularly 1 to 20 atmospheres can be used, and when hydrogenating comparable pressures can be employed. In the case of isomerization, similar conditions can be employed. In any case, sufiicient pressure is employed to have the reactant or reactants present in liquid phase during reaction.

Products resulting from dimerization, isomerization and hydrogenation reactions carried out in accordance with the invention find utility in well-known manner, and, for purposes of illustration, as follows.

(1) Ethylene is dimerized to n-butene (a mixture of 1 and 2 n-butenes) which finds use in the alkylation of isobutane in the production of motor fuels.

(2) 2-methylbutene-l is isomerized to Z-methylbutene- 2 which is prefered for isoprene synthesis.

(3) Lube stocks containing olefins are subjected to by drogenation to increase stability.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Catalyst preparation Upon admixing butyl lithium and cobalt (III) acetylacetonate in benzene solution under nitrogen, and in atomic ratios Li:Co(IH) ranging from 4 to 7, a dark brown mixture was formed, and a hydrocarbon gas was evolved. The catalyst system formed was a combination or complex of the reactants. High catalytic activity for dimerization and hydrogenation reactions was observed over the above range of atomic ratios, with ratios of Li:Co(III) of about 5-7 being outstanding.

The catalyst system was several times more active when the cobalt and lithium containing reagents were admixed in the presence of ethylene over the above atomic 3 ratio range of from 4 to 7, particularly high catalytic activity for dimerization and hydrogenation reactions again being observed over the range of atomic ratios Li:Co(III) of about 5-7.;

The atomic ratio of Li:Co is not particularly critical in the case of isomerization reactions, the reaction rate being quite fast, indicating that the rate limiting step is somewhat a function of dilfusion of the olefin into the catalyst complex. As an example, high reaction rates were observed with atomic ratios of Li:Co(III) ranging over 2-6. 7

Upon admming butyi lithium 'and cobalt (II) acetylacetonate under the above conditions, the resulting catalyst system exhibits similar characteristics, except that for dimerizati-on and Hydrogenation reactions, the atomic ratidrange of high catalytic activity is Li:Co(II) of 3-5. This'ratio range is less critical in the case of isomerization; the reaction rate'again being quite fast. l:

Similar results are obtained when other LiR compounds of the invention are substituted for butyl lithium.

The following examples illustrate the preparation of the' catalyst complexes of the invention.

Example l.A preformed catalyst complex for use in} dimerization, isomerization and hydrogenation reactions was made introducing a '20 ml. position of a .975 molar solution of cobalt (III) acetyiacetonate in toluene into a flask under nitrogen. To this solution were added 5.5 ml. of a 1.63 molar solution of butyl lithium in hexane. A deep brown solution was formed comprised of the catalyst complex, useful for the various purposes set forth herein.

Example 2.-A catalyst complex for use in the dime-rization of ethylene was made by introducing a 20 mi. portion of a .075 molar solution of cobalt (III) acetylacetonate in benzene into a flask under ethylene at 10 p.s.i.g. To this solution were added 5.5 ml. of a 1.63 molar solution of butyl lithium in hexane. A deep brown solution was formed comprised of the catalyst complex.

Example 3.--A catalyst complex for use in the dimerization of ethylene was made by introducing a 20 ml. portion of a .075 molar solution of cobalt (Ii) acetyl acetonate in benzene into a flask under ethylene at 10 p.s.i.g. To this solution were added 3.7 ml. of a 1.63 molar solution of butyl lithium in hexane. A deep brown solution was formed comprised of the catalyst complex.

Example 4.A catalyst complex for .use in dimerization, isomerization and hydrogenation reactions was made by introducing a 20 ml. portion of a .075 molar solution of cobalt (II) acetylacetonate in a suitable solvent, e.g., benzene or toluene, into a flask under nitrogen. To this solution were added 3.7 ml. of a 1.63 molar solution of butyl lithium in hexane. The solution formed comprised the catalyst complex.

Example 5.A catalyst complex was prepared in situ under an atmosphere of hydrogen by adding 6.8 ml. of benzene, to 2.7 ml. of a .37 molar solution of cobalt (III) acetylactonate in benzene, 10.5 ml. of 2-methylbutene-l, and 3.7 m1. of 1.6 molar butyl lithium in hexane in that order to a flask. A dark brown solution formed which began to absorb hydrogen rapidly.

Any other LiR compound as hereinbefore specified can be substituted in the above examples for the butyl lithium employed.

Dimerization The data of Table I are the result of runs made with a series of preformed catalyst complexes in benzene as solvent, the atomic ratio of lithium to cobalt (III) in the complexes varying as shown. The lithium compound was butyl lithium. The concentration of catalyst complex in its solution in benzene was approximately .06 molar. A good general range is from .01 to .1 moiar. After formation of the complex, which took place in a closed container in a nitrogen atmosphere, ethylene was passed into the solution, whereupon a mixture of normal butenes was formed with practically complete exclusion 4 of higher, oligomers. The runs were carried out at 30 C. for a period of minutes under an ethylene pressure of 50 p.s.i.g.

TABLE I C H moles/gram The data of Table I clearly demonstrate high catalytic activity in the atomic ratio range of Li:Co of 4-7 in dimerization reactions. f

The data of TableII are the result of runs made with a series of catalyst complexes prepared from butyl lithium and cobalt (III) acetylacetonate in benzene as solvent, and in the presence of ethylene at 10 p.s.i.g. Ethylene was thereafter passed into the solution for 240 minutes at 30 C., and under a pressure of 50 p.s.i.g. A mixture of normal butenes was formed, with the practically compiete exclusion of higher oligomers. The concentration of catalyst in benzenes at the beginning of each run was approximately .05 molar. Increased activity of the catalyst when prepared in the .preSenceEOf ethylene is clearly demonstrated, as is high catalytic activity in the atomic ratio range of Li:Co(III) of 4-7 in dimerization reaction.

Other hydrocarbon solvents can be substituted for benzene, although some change in yield may be experienced, e.g., the yields with toluene and cyclohexane, respectively, were somewhat lower, but nevertheless practical.

A gradual decrease of catalytic activity was observed during the course of several hourscThis rate decline was accompanied by the formation of an insoluble black solid. However, it was observed that catalyst upon becoming inactive could be regenerated by the addition of more LiR.

The runs of Table III were made with preformed catalyst complexes made in benzene and under nitrogen between butyl lithium and cobalt (II) acetylacetonate. Thereafter, ethylene was passed into the solution at 30 C. for 120 minutes, and under a pressure of 50 p.s.i.g. A mixture of butenes was formed to the practical exclusion of higher oligomers. The concentration of catalyst in benzene at the beginning of each run was approximately .05 molar. These data show high catalyst activity between atomic ratios of Li:Co(II) of 3 to 5.

Dimerization of butadiene-1,3 is demonstrated in the following example.

Example IV.Into a solution of catalyst complex in benzene prepared as in Example Land in which complex the atomic ratio of lithium to cobalt (III) was 6.0, was fed butadiene-1,3 at a temperature of 30 C. and a pressure of 50 p.s.i.g. for 120 minutes. The product consisted of a mixture in which 3-methyl-l,4,6-heptatriene heavily predominated. This material is a valuable component in preparation of ethylene-propylene terpolymer.

Recovery of dimer product from the respective reaction The presence of an alkyl group or groups on vinylic carbon atoms inhibits the rate of reaction, as shown in Table VI. This apparently is a cause for the accumulation of normal 2-olefins formed during the isomerization of normal l-olefins. Also note that the isomerization of 2- masses of the above runs was accomplished in a convenmethylpentene-l is considerably slower than that of tional manner, e.g., by adding water or a monohydric hcxene-1.

aliphatic alcohol to the reaction mass to kill the catalyst, On the other hand, it is to be noted that the presence followed by filtering to remove any solids, and then disof an alkyl group on a carbon atom Which is not included tillation to remove solvent and dimer product. in the double bond has a minor effect on the reaction rate,

Isomerization as, for exmaple, in the case of 4-methylpentene-l.

As brought out above, the new catalysts of the invention also induce double bond isomerization of olefins, and un- TABLE VI like many other catalyst systems, these new catalysts pro- Relative mote such double bond migration with the virtually corn- Olefin reactivity Principal product plete exclusion of skeletal isomerization, polymerization 1 10 Emma. and/01' cracking, Hexene-2 1 Hexene-3.

The isomerization of l-olefins proceeds with an excep- 3 tionally high rate. Because of this high activity, the effeet of catalyst composition is less pronounced than in the case of dimerization. Nevertheless, outstandingly high activity is still discernible within the Li:Co ratio ranges set Hi h catalyst l i i f hi type fi d use f forth above for dimeriZatiOn feactioflsisomerizing selected olefins to yield predominantly one Other unusual features of catalyst selectivity are present. product, or for isomerizing selectively .or predominantly AS Will be Seen from the fOHOWiIIg- Tables IV and V, a certain component or components present in olefin the isomerization of higher normal l-olefins proceeds in a mixtures stepwise manner, but does not rapidly reach equilibrium. Hydrogenation Instead, 2-olefin (cis and trans) accumulates, 3-olefin (in the case of C and higher olefins) being formed much The catalyst complexes of the invention also catalyze more slowly, since the 2-olefin is far less reactive under the hydrogenation of olefins. The complexes are soluble reaction conditions that the terminal olefin. Moreover, the in hydrocarbons, and the substrate itself, if liquid, can 2-olefin is formed with a cis selectivity somewhat greater serve as a solvent. On the other hand, any of the usual than that of the equilibrium value during early stages of paraffinic or aromatic hydrocarbon solvents can be emthe reaction. ployed whether the substrate is solid or liquid.

Some 3-olefin is formed (where possible) early in the In fact, the catalyst complexes of the invention, in reaction, but further isomerization of 2-olefin proceeds solution, can be employed for the hydrogenation of only slowly. Apparently, the 3-olefin is formed directly macromolecular, colloidal or insoluble substrates. from the l-olefin more rapidly than from the 2-olefin. These catalyst complexes are so active that hydro- Isomerization of 3-olefin (where possible) is extremely genations can be conducted at a useful rate even under slow, except at high temperatures. ordinary conditions of temperature and pressure as illus- In the following Table IV is illustrated the isomerization trated in Table VII. In carrying out these reactions, 0.10 of heptene-l over a range of atomic ratios Li:Co(III) mole of olefin was contacted with 5 l0 mole cobalt of 4-8. The reactions were carried out at ambient (room) (III) acetylacetonate and 3X 10- mole of butyl lithium temperature, and over variable periods of time, as shown. at 30 C. under one atmosphere of hydrogen. The LizCo The lithium compound was butyl lithium. atomic ratio was 6.

TABLE IV Product composition Time, Cis-Z- Trans- Percent Li:C0(III) min l-olefin olefin 2-olefin 3-olefin reacted (Dis/trans 15 a3 20 47 e7 .43 15 20 22 4c 12 so .48 15 64 12 24 36 .50 5 27 54 14 95 .50 180 4 2s 54 1s 96 .48

The data of Table V on the isomerization of heptene-l TABLE VII were obtained with a catalyst complex prepared with an 60 atomic ratio of Li:Co(IlI) of 6. The reactions were carcomposition ried out at ambient (room) temperature, and over variable Time, 2 3 periods of time as shown. The lithium compound was Olefin lefin 016ml Paraffin butyl lithium. Heptene-l and -3 (equi- 10 4 57 39 molecular) 30 0 55 45 TABLE v Octane-2 8 g 13 Product composition 120 0 42 58 Cis-2- Trans- Percent; zmethyl'butenel 5 Time min. l-olefin olefin 2-olefin 3-olefin reacted Cis/trans 60 37 42 21 f 6 Olefin structure, as will be seen from the above Table 0 17 53 30 VII, greatly influences the rate of hydrogenation. The

0 11 52 37 100 75 most reactive olefins are those with the smallest number of alkyl groups substituted on the carbon atoms containing the unsaturated linkage. Thus heptene-l is considerably more reactive than heptene-Z, octene-2, heptene-3 and 2-methylbutene-1 and -2.

The data of Table VII show that the isomerizing activity of the catalyst is retained in the presence of hydrogen, for l-olefins are converted to 2-olefins in a competitive process, the end product, nevertheless, being the corresponding parafiin.

The effect of the atomic ratio of Li:Co upon catalytic activity is shown by the data of Table VIII. In carrying out these reactions, 0.10 mole of olefin and 10- mole of cobalt (III) acetylacetonate in admixture with butyl lithium in the atomic ratios shown were contacted for 30 minutes at 30 C. with hydrogen under 30 p.s.i.g. The olefin was heptene-l.

As with the dimerization and isomerization activity of the catalyst complex when comprised of hydrocarbyl lithium and cobalt (III) acetylacetonate, superior hydrogenation activity is observed in the range of atomic ratios of LizCo (III) of 4-7, and particularly at or about 6. In the case of cobalt (H) acetylacetonate, the range is 3-5, with particularly high activity at or about 4.

The rate of hydrogenation increases as temperature and/or pressure is elevated. The influence of pressure can be seen upon comparison of the data of Table VII above with that of Table IX below. In carrying out the reactions of Table IX, 0.10 mole of olefin, 5X10- mole of cobalt (III) acetylacetonate, and 3 10- mole of butyl lithium were contacted at 30 C. for minutes under hydrogen pressure of 30 p.s.i.g.

TAB LE IX Product composition Olefin l-olefin 2(3)-olefin Paraffin Heptene-l and -3 (equimo1ecular). 0 41 59 Octene-Z 0 56 44 2 -methy1bntene-l 35 38 27 Whil low hydrogen pressures are normally more convenient, higher pressures can be used to provide accelerated rates.

The catalysts of the invention are sensitive to atmospheric air, water, and hydroxylic solvents, and it therefore is highly preferred that these materials be rigorously excluded. 1

Similar data and results are obtained when other hydrocarbyl lithium compounds are substituted for those employed in obtaining the data of the above tables and examples.

Also cobalt (III) and cobalt (II) acetylacetonates can be used interchangeably in the above examples, attention being given to the preferred atomic ratio ranges set forth above, and in obtaining data comparable to the data of the above tables.

Likewise other monoolefins and diolefins can be substituted.

I claim:

1. Process for the hydrogenation of olefins which comprises contacting an olefin with hydrogen under hydrogenation conditions in the presence of a catalyst system obtained by directly admixing (a) a hydrocarbyl lithium compoundv of the formula LiR wherein R is an alkyl or cycloalkyl radical having 1-30 carbon atoms, with (b) a cobalt acetylacetonate of the formula Co[CH-( 3)z]n wherein n has a value of 2 or 3,

the proportion of said hydrocarbyl lithium compound to said cobalt acetylacetonate so admixed corresponding to an atomic ratio of LizCo in the range of 3-5 when n is 2 and in the range of 4-7 when n is 3.

2. Process according to claim 1 wherein n is 2 and the LizCo ratio is 3-5.

3. Process according to'claim 2 wherein LiR is an UNITED STATES PATENTS 3,393,245 7/1968 Zuech 260-680 3,412,174 11/1968 Kl'Oll 260-6839 3,439,054 4/1969 KrOll 260 666 3,481,961 12/1969 Pregaglia et a1. 260-6839 HERBERT LEVINE, Primary Examiner US. Cl. X.R. 

